CN106906442B

CN106906442B - A kind of coating with high hardness and self-lubrication and preparation method thereof

Info

Publication number: CN106906442B
Application number: CN201510982935.9A
Authority: CN
Inventors: 李金龙; 王越; 王永欣; 王立平
Original assignee: Ningbo Institute of Material Technology and Engineering of CAS
Current assignee: Ningbo Institute of Material Technology and Engineering of CAS
Priority date: 2015-12-23
Filing date: 2015-12-23
Publication date: 2019-05-10
Anticipated expiration: 2035-12-23
Also published as: CN106906442A

Abstract

The present invention provides a coating with high hardness and self-lubricating properties. The coating combines the amorphous nanocrystalline structure with high strength and toughness with the MAX phase layered structure, and utilizes the good self-lubricating property of the MAX phase layered structure, so that the coating not only has high hardness, but also has good self-lubricating properties , can meet the anti-friction and wear-resistant protection requirements of key components and tooling and other substrates. In addition, for the coating composed of the MAX phase layered structure of nanocrystalline TiN, amorphous Si ₃ N ₄ and Ti-Si-C three elements, the present invention utilizes the multi-arc ion plating technology to prepare the coating, and the obtained coating The layer hardness can reach 30‑40GPa, and the friction coefficient can reach 0.1‑0.2.

Description

A kind of coating and preparation method thereof with high rigidity and self-lubrication

Technical field

The present invention relates to a kind of technical field of surface more particularly to a kind of coatings with high rigidity and self-lubrication And preparation method thereof.

Background technique

Currently, equipment manufacture just develops towards high speed, high load, high-accuracy and green processing direction, to equipment key portion The reliability and long-life of part and tool and mould are also put forward higher requirements.Develop the surface peening of Advanced Equipment critical component and prevents Shield technology is to reduce equipment critical component friction power loss, extend service life and improve the key technology of functional reliability.

The hard coats such as titanium-based, the chromium base obtained using physical gas phase deposition technology can be used for tool and mould and equipment key portion The surfacecti proteon of part, and obtain good protection effect.However, although the hard coat hardness of these systems is sufficiently high, It is that friction reducing effect is undesirable.On the other hand, although the antifriction self-lubricating performance of some coatings is preferable, its hardness is not high, example Such as MoS₂Coating has good antifriction self-lubricating performance, but its hardness is not high.

Therefore, exploring a kind of high rigidity and the coating of low-friction coefficient of having both is one of research topic of scientific worker, It can be applied to the anti-friction wear-resistant protection of equipment key components and parts and tool and mould.

Summary of the invention

Status in view of the above technology, the present invention is intended to provide a kind of coating with high rigidity and self-lubrication.

In order to achieve the above technical purposes, the present inventor is after a large amount of exploratory developments, by the amorphous with high-strength tenacity Nanocrystalline structure is combined with MAX phase layer structure, and the MAX phase layer structure refers to ternary layered ceramic M_n+1AX_n(n=1- 6) structure, referred to as MAX phase, wherein M is magnesium-yttrium-transition metal, and A is major element, and X is C or N element.These MAX same genus six Prismatic crystal system, crystal structure can be described as M₆X octahedron and A atomic layer interval stacking.Between M-X mainly with strong covalent bond and Ionic bond combines, and the combination between M-X and A atom is weaker.On the one hand this unique bonding pattern makes MAX phase ceramics With the excellent machinability of metal material and thermally conductive, electric conductivity；On the other hand again with anticorrosive, the antioxygen of ceramic material The characteristics such as change；Meanwhile unique nanometer laminated structure imparts the good self-lubrication of MAX phase ceramics and certain damage is held Limit.As lubricant, lubricant effect can compare favourably with common solid lubricant graphite, molybdenum disulfide etc.；And damage tolerance is then Make it that can bear certain deformation at normal temperature and brittle fracture will not occur, MAX phase is even more to have preferable plasticity at high temperature. Therefore, it when nanocrystalline structure is combined with MAX phase layer structure, since MAX phase layer structure has good self-lubrication, obtains To coating not only there is high rigidity, but also there is good self-lubricating property, can satisfy equipment key components and parts and work mould The anti-friction wear-resistant protection requirements of the matrixes such as tool.

That is, technical solution proposed by the present invention are as follows: a kind of coating with high rigidity and self-lubrication, it is characterized in that: institute Stating includes the amorphous nano crystal structure with high-strength tenacity in coating, also includes MAX phase layer structure.

The MAX phase include but is not limited to 211 phases, 312 phases, 413 phases, 514 phases, 615 phases, 716 phases, 523 phases or Any one of 725 phases or wherein several combinations.

Wherein, 211 phases include but is not limited to Ti₂AlC、Ti₂AlN、Hf₂PbN、Cr₂GaC、V₂AsC、Ti₂InN、Nb₂AlC、 (Nb,Ti)₂AlC、Ti₂AlN_0.5C_0.5、Nb₂GaC、Nb₂AsC、Zr₂InN、Ti₂GeC、Cr₂AlC、Zr₂SC、Mo₂GaC、Ti₂CdC、 Hf₂InN、Zr₂SnC、Ta₂AlC、Ti₂SC、Ta₂GaC、Sc₂InC、Hf₂SnN、Hf₂SnC、V₂AlC、Nb₂SC、Ti₂GaN、Ti₂InC、 Ti₂TIC、Ti₂SnC、V₂PC、Hf₂SC、Cr₂GaN、Zr₂InC、Zr₂TIC、Nb₂SnC、Nb₂PC、Ti₂GaC、V₂GaN、Nb₂InC、 Hf₂TIC、Zr₂PbC、Ti₂PbC、V₂GaC、V₂GeC、Hf₂InC、Zr₂TIN。

312 phases include but is not limited to Ti₃AlC₂、Ti₃GeC₂、Ti₃SiC₂、Ti₃SnC₂、Ta₃AlC₂、(V_0.5Cr_0.5)₃AlC₂、 V₃AlC₂、Ta₃Al_0.6Sn_0.4C₂。

413 phases include but is not limited to Ti₄SiC₃、Ti₄GaC₃、Ti₄GeC₃、α-Ta₄AlC₃、β-Ta₄AlC₃、Nb₄AlC₃、 V₄AlC₃、(V,Cr)₄AlC₃。

514 phases include but is not limited to (Nb_0.5Ti_0.5)₅AlC₄。

615 phases include but is not limited to β-Ta₆AlC₅。

716 phases include but is not limited to Ti₇SnC₆。

523 phases include but is not limited to (V_0.5Cr_0.5)₅Al₂C₃、Ti₅Al₂C₃、Ti₅Si₂C₃、Ti₅Ge₂C₃。

725 phases include but is not limited to Ti₇Si₂C₅、Ti₇Ge₂C₅。

The amorphous nano-crystalline structural material with high-strength tenacity is unlimited including titanium-based amorphous nanocrystalline or chromium base The hard materials such as amorphous nano-crystalline.

As a kind of implementation, the amorphous nano crystal structure with high-strength tenacity is nanocrystalline TiN and amorphous Si₃N₄The nano composite structure of composition；The MAX phase layer structure is the MAX phase stratiform being made of tri- kinds of elements of Ti-Si-C Structure, including Ti₄SiC₃、Ti₃SiC₂、Ti₅Si₂C₃、Ti₇Si₂C₅Deng one of or two or more mixing.At this point, described The hardness of coating is up to 30-40GPa, and coefficient of friction is up to 0.1-0.2.The present inventor additionally provides a kind of using multi-arc ion coating The method that physical gas phase deposition technology prepares the coating, specific as follows:

(1) matrix of coating to be deposited is subjected to surface cleaning processing, is then fed into vacuum chamber and carries out forvacuum, and Keeping vacuum room temperature is 350-450 DEG C；

In the step (1), surface cleaning processing method is unlimited, including cleaned by ultrasonic vibration etc.；

Preferably, vacuum degree is lower than 3 × 10 after vacuum chamber carries out forvacuum processing in the step (1)^-3Pa；

(2) it is filled with inert gas argon gas, using multi sphere ion plating technology etching described matrix surface；

In the step (2), the target that when etching uses is unlimited, can be pure titanium target material, titanium silicon target or silicon target Material bombards target under high bias using multi sphere ion plating technology, to have the function that etch described matrix surface；

In the step (2), preferably, etching bias used is 900-1200V；.

In the step (2), preferably, preferably, the target current is controlled in 40-50A；.

In the step (2), preferably, the etch period is 5-10min；

In the step (2), preferably, etching is more than three times, etching bias gradually increases from low to high, further The etch period 2-3min preferably under each bias condition；

(3) pure titanium target material is used, reaction gas is acetylene or nitrogen, utilizes multi sphere ion plating technology depositing Ti C transition Layer or TiN transition zone；

In the step (3), preferably, the purity of pure titanium target material is more than or equal to 99.9at.%；

In the step (3), preferably, TiC transition zone or TiN transition zone with a thickness of 100-200nm；

In the step (3), preferably, nitrogen pressure is 0.5-5Pa, target current 60-80A, substrate bias is 70-120V, depositing temperature are 350-450 DEG C；

In the step (3), preferably, acetylene air pressure is 0.5-5Pa, target current 60-80A, substrate bias is 70-120V, depositing temperature are 350-450 DEG C；

(4) TiSi target is used, reaction gas is the mixed gas of acetylene and nitrogen, is deposited using multi sphere ion plating technology The coating takes out after furnace cooling；

In the titanium silicon target, the mass percentage content of element silicon is 5-15%；

In the deposition process, air pressure 0.5-5Pa, target current 60-80A, substrate bias 10-40V, deposition temperature Degree is 400-450 DEG C；

(5) vacuum or protective atmosphere heat treatment, heat treatment temperature 600- will be carried out through step (4) treated matrix 1000℃。

In the step (5), preferably, heat treatment time is 1-3 hours.

In conclusion the present invention combines the amorphous nano crystal structure with high-strength tenacity with MAX phase layer structure To a kind of new coating structure, the good self-lubrication having using MAX phase layer structure makes coating not only have high rigidity, And there is good self-lubricating property, the anti-friction wear-resistant protection that can satisfy the equipment matrixes such as key components and parts and tool and mould needs It asks.In addition, for by nanocrystalline TiN, amorphous Si₃N₄And the coating that the MAX phase layer structure of tri- kinds of elements of Ti-Si-C is constituted, The present invention prepares the coating using multi sphere ion plating technology, has the following beneficial effects:

(1) multi sphere ion plating technology is utilized, by selection TiSi target, is filled with acetylene and nitrogen, and control sedimentary condition, I.e. control depositing temperature is 400-450 DEG C, substrate bias 10-40V, target current 60-80A and deposition pressure are 0.5- 5Pa, not only deposition obtains nanocrystalline TiN and amorphous Si₃N₄, and the MAX phase layer structure of tri- kinds of elements of Ti-Si-C is obtained, because And improve the self-lubricating property of coating；

(2) subsequent vacuum or protective atmosphere heat treatment are carried out by the coating to deposition, further promoted in coating Formation with layer structure MAX phase；

(3) high rigidity and self-lubrication are had both using the coating that this method deposits, hardness is rubbed up to 30-40GPa Coefficient is wiped up to 0.1-0.2.

Detailed description of the invention

Fig. 1 is the transmission electron microscope picture of TiSiCN coating made from the embodiment of the present invention 1；

Fig. 2 is the hardness of TiSiCN coating made from the embodiment of the present invention 1 with the change curve of depth；

Fig. 3 is the friction coefficient curve of TiSiCN coating made from the embodiment of the present invention 1.

Specific embodiment

Present invention is further described in detail with embodiment with reference to the accompanying drawing, it should be pointed out that reality as described below It applies example to be intended to convenient for the understanding of the present invention, and does not play any restriction effect to it.

Embodiment 1:

In the present embodiment, the coating with high rigidity and self-lubrication includes by nanocrystalline TiN and amorphous Si₃N₄It constitutes Amorphous nano-crystalline composite construction with high-strength tenacity further includes the MAX phase layer structure of tri- element of Ti-Si-C.

In the present embodiment, above-mentioned coating is prepared using multi sphere ion plating technology, specifically includes the following steps:

(1) the titanium alloy test piece sample of coating to be deposited is subjected to mechanical lapping polishing, is then carried out in acetone reagent Cleaned by ultrasonic vibration, sample clean 3 times, the sample after cleaning air-dries；

(2) sample is sent into vacuum chamber, vacuum chamber carries out forvacuum to back end vacuum degree 1 × 10^-3Pa, in forvacuum During vacuum chamber is heated, heating temperature is to 450 DEG C；

(3) after back end vacuum and heating temperature reach requirement, it is filled with inert gas argon gas, is splashed using multi sphere ion plating technology Penetrate cleaning pure Ti target 2min, ion sputtering etch cleaner sample 5min；

(4) pure titanium target material (target purity 99.9at.%) is used, is filled with reaction gas nitrogen, utilizes multi-arc ion coating skill Art, adjustment air pressure are 0.5Pa, and target current 60A, matrix is bias 70V, in sample surfaces depositing TiN transition zone；

(5) titanium silicon target is used, wherein the mass percentage content of element silicon is 5-15%, and reaction gas is acetylene and nitrogen The mixed gas of gas, using multi sphere ion plating technology, adjustment air pressure is 0.5Pa, target current 60A, substrate bias 40V, is sunk Accumulated temperature degree is 450 DEG C, sedimentation time 2h, in TiN transition layer surface depositing coating, then cools to 200 DEG C or less with the furnace and takes Out；

(6) 800 DEG C will be carried out vacuum heat treatment 1 hour through step (5) treated sample.

Through the above-mentioned coating being prepared using its result of its microstructure of transmission electron microscope observing as shown in Figure 1, being shown in It forms that TiN is nanocrystalline and Si3N4 amorphous phase in coating, while observing the presence of stratiform MAX phase.

The above-mentioned coating being prepared is subjected to hardness test, test method are as follows: use nano-hardness tester continuous stiffness measurement It is tested, the hardness of the coating is with the curve of change in depth as shown in Fig. 2, showing that the hardness of the coating is up to 38GPa.

The above-mentioned coating being prepared is subjected to frictional behaviour test, test method are as follows: utilize UMT friction wear testing machine It is tested, the friction coefficient curve of the coating is as shown in figure 3, show that the coefficient of friction of the coating is about 0.15.

Embodiment 2:

(2) sample is sent into vacuum chamber, vacuum chamber carries out forvacuum to back end vacuum degree 1 × 10^-3Pa, in forvacuum During vacuum chamber is heated, heating temperature is to 400 DEG C；

(4) pure titanium target material (target purity 99.9at.%) is used, being filled with reaction gas is acetylene, utilizes multi-arc ion coating Technology, adjustment air pressure are 2Pa, and target current 80A, matrix is bias 40V, in sample surfaces depositing Ti C transition zone；

(5) titanium silicon target is used, wherein the mass percentage content of element silicon is 5-15%, and reaction gas is acetylene and nitrogen The mixed gas of gas, using multi sphere ion plating technology, adjustment air pressure is 3Pa, target current 70A, substrate bias 30V, deposition Temperature is 400 DEG C, sedimentation time 2h, in TiC transition layer surface depositing coating, then cools to 200 DEG C or less taking-ups with the furnace；

(6) 700 DEG C will be carried out vacuum heat treatment 1 hour through step (5) treated sample.

, the display similar to Figure 1 using its result of its microstructure of transmission electron microscope observing through the above-mentioned coating being prepared It forms that TiN is nanocrystalline and Si3N4 amorphous phase in the coating, while observing the presence of stratiform MAX phase.

The above-mentioned coating being prepared is subjected to hardness test, test method is same as Example 1, measures the hard of the coating Degree shows that the hardness of the coating is up to 36GPa with the curve similar to Figure 2 of change in depth.

The above-mentioned coating being prepared is subjected to frictional behaviour test, test method is same as Example 1, measures the coating Hardness with the curve similar to Figure 3 of change in depth, show that the coefficient of friction of the coating is about 0.12.

Technical solution of the present invention and beneficial effect is described in detail in embodiment described above, it should be understood that Above is only a specific embodiment of the present invention, it is not intended to restrict the invention, it is all to be done in spirit of the invention Any modification and improvement etc., should all be included in the protection scope of the present invention.

Claims

1. a kind of preparation method of the coating with high hardness and self-lubricity is characterized in that: comprise nanocrystalline TiN, amorphous Si ₃ N ₄ in the described coating, and be made up of three kinds of elements of Ti-Si-C The MAX phase layered structure;

Adopt multi-arc ion plating physical vapor deposition technology, which specifically includes the following steps:

(1) The substrate on which the coating is to be deposited is subjected to surface cleaning treatment, and then sent to a vacuum chamber for pre-evacuation, and the temperature in the vacuum chamber is kept at 350-450 °C;

(2) Filling with inert gas argon, using multi-arc ion plating technology to clean and etch the surface of the substrate;

(3) Using pure titanium target material, the reaction gas is acetylene or nitrogen, and using multi-arc ion plating technology to deposit TiC transition layer or TiN transition layer;

(4) adopt TiSi target material, the reaction gas is the mixed gas of acetylene and nitrogen, utilize multi-arc ion plating technology to deposit described coating, and then take out after cooling with the furnace;

In the titanium-silicon target, the mass percentage of silicon is 5-15%;

In the deposition process, the air pressure is 0.5-5Pa, the target current is 60-80A, the substrate bias voltage is 10-40V, and the deposition temperature is 400-450°C;

(5) The substrate treated in step (4) is subjected to vacuum or protective atmosphere heat treatment, and the heat treatment temperature is 600-1000°C.

2. The method for preparing a coating with high hardness and self-lubricity as claimed in claim 1, wherein the MAX phase comprises Ti ₂ SC, Ti ₃ SiC ₂ , Ti ₄ SiC ₃ , Ti ₅ Si Any one of ₂ C ₃ , Ti ₇ Si ₂ C ₅ or a combination of several of them.

3 . The method for preparing a coating with high hardness and self-lubricity as claimed in claim 1 , wherein the hardness of the coating is 30-40 GPa and the friction coefficient is 0.1-0.2. 4 .

4. The method for preparing a coating with high hardness and self-lubricity as claimed in claim 1, wherein in the step (2), the target material used during etching is a pure titanium target material, a titanium Silicon target or silicon target.

5 . The method for preparing a coating with high hardness and self-lubricity as claimed in claim 1 , wherein in the step (2), the bias voltage used for etching is 900-1200V. 6 .

6 . The method for preparing a coating with high hardness and self-lubricity as claimed in claim 1 , wherein in the step (2), the target current is controlled at 40-50A. 7 .

7 . The method for preparing a coating with high hardness and self-lubricity as claimed in claim 1 , wherein in the step (2), the etching time is 5-10 min. 8 .

8. The method for preparing a coating with high hardness and self-lubricity as claimed in claim 1, wherein in the step (2), etching is performed more than three times, and the etching bias is gradually increased from low to high. Increase.

9 . The method for preparing a coating with high hardness and self-lubricity according to claim 7 , wherein in the step (3), the purity of the pure titanium target is greater than or equal to 99.9 at.%. 10 .

10 . The method for preparing a coating with high hardness and self-lubricity as claimed in claim 1 , wherein in the step (3), the thickness of the TiC transition layer or the TiN transition layer is 100-200 nm. 11 .

11. The preparation method of the coating with high hardness and self-lubricity as claimed in claim 1, characterized in that: in the step (3), the nitrogen gas pressure is 0.5-5Pa, and the target current is 60-80A, The substrate bias is 70-120V, and the deposition temperature is 350-450°C.

12. The method for preparing a coating with high hardness and self-lubricity as claimed in claim 1, wherein in the step (3), the acetylene gas pressure is 0.5-5Pa, and the target current is 60-80A, The substrate bias is 70-120V, and the deposition temperature is 350-450°C.

13 . The method for preparing a coating with high hardness and self-lubricity as claimed in claim 7 , wherein in the step (5), the heat treatment time is 1-3 hours. 14 .